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Department of Chemistry,
Narain (PG) College Shikohabad, U. P., INDIA.
*2
Department of Chemistry,
Indian Institute of Technology Kanpur, Kanpur, U. P., INDIA.
(Received on: September10, 2013)
ABSTRACT
Present study is devoted to understand the molecular interactions
in EAA-THF binary liquid mixture using steady-state UV-Vis and
fluorescence spectroscopy, fourier transform infrared spectroscopy
(FT-IR) and proton-nuclear magnetic resonance (1H NMR)
measurements. The deviation in the absorption as well as emission
maximum of R6G in EAA-THF binary mixture has been
explained in terms of molecular interactions between solvent
molecules in the ground as well as excited state, respectively. The
increase in the stretching frequency of carbonyl group of EAA in
presence of THF as well as the observed H1 NMR chemical shift
in the upfield region in EAA-THF binary mixture have also been
used to explain the molecular interactions in the binary liquid
mixture.
Keywords: Binary mixture, Molecular interactions, Ethylacetoacetate, Tetrahydrofuran and Rhodamine 6G.
1. INTRODUCTION
On mixing the different solvents, the
unique behaviour of binary mixture
compared to its constituent counterpart is
believed to be arise from the nature of
solvent-solvent interaction. On this purview,
the interaction in binary liquid mixtures is a
subject of great interest among the
Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
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PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
spectrofluorometer(Fluoromax
4,
JobinYvon) respectively using a 10 mm
quartz cuvette. FT-IR spectra have been
measured by FTIR, PerkinElmer, USA. 1H
NMR spectra of the samples were measured
by commercial spectrometer JEOL, ECX400, Japan operating at 400 MHz and
tetramethylsilane was used as reference. All
the experiments have been performed at
room temperature.
3. RESULTS AND DISCUSSION
3.1 Steady-state UV-Vis and Fluorescence
Spectroscopic Study
The absorption and emission spectra
of 1 M R6G have been recorded in pure
EAA and THF and their mixtures different
compositions of the solvents and are shown
in figure 1a and 1b. Here we have taken very
small concentration of R6G to avoid solutesolute interactions so that we can get the
information of solvent-solvent interaction
more precisely. The absorption spectrum of
R6G in pure THF and EAA shows an
absorption maximum at 534 nm and 528.8
nm respectively. However the emission
maximum has been observed as 550.5 nm
and 554 nm in pure THF and EAA
respectively. Figure 2a shows the change in
the absorption maximum of R6G as a
function of mole fraction of THF in EAATHF binary mixture. Here the change in the
absorption maximum of R6G in EAATHFmixture on increasing the mole fraction
of THF is not linear. It shows a deviation
towards shorter wavelength side in EAATHF binary mixture. The change in the
emission maximum of R6G in the binary
mixture also shows a deviation towards
shorter wavelength as shown in figure 2b.
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Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
272
PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
2.2077 (s), 3.4869 (s), 4.16-4.127 (q), 1.2461.2108 (t). Where, the peak at 3.4869 in pure
EAA is corresponds to the proton (H1) of
active methylene group. In presence of 90 %
THF (vol/vov) the obs of EAA become
shifter towards upfield region and were
observed at 2.1674-2.1625 (d), 3.42093.4136 (d), 4.1393-4.0856 (q), 1.23641.2010 (t), respectively. Here, the first two
peaks are doublet (singlet in pure EAA) is
due to the presence of obs of pure THF in
the same region. The shifting towards
upfield region of all chemical shift of EAA
in presence of THF also indicates a change
in the extent of molecular interactions in
EAA-THF binary mixture.
Figure 1.Normalized steady state (a) absorption and (b) emission spectra of R6G in EAA-THF binary
liquid mixtures. The absorption and emission spectra of R6G in pure solvents are represented as ( )
for EAA and () for THF.
Figure 2. The change in the (a) absorption and (b) emission maximum of R6G with error bars plotted
against mole fraction of THFin EAA-THF binary mixtures. Solid black line represents the ideal change.
Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
273
Figure 3.FT-IR stretching bands of carbonyl group of EAA in EAA-THF binary liquid mixture at different
compositions. Black dotted, green, blue dashed, red, and blue lines in this figures are for 0 %, 40 %, 90 %,
95 %, 100 % (vol/vol) THF in EAA-THF binary liquid mixtures, respectively.
Figure 4.1HNMR spectra of (a) pure THF, (b) pure EAA and (c) EAA- THF binary liquid mixtures.
Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
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PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
4. CONCLUSION
In the present study, spectroscopic
methods have been employed to understand
the molecular interactions in EAA-THF
binary liquid mixture. The deviation in the
absorption as well as emission maximum of
R6G towards shorter wavelength in EAATHF binary liquid mixture has been
observed, which causes to decrease in the
polarity in the binary mixture to the close
proximity of R6G and is responsible for
decrease in the molecular interactions
between the solvent molecules. The change
in the stretching frequency of carbonyl
group of EAA towards higher wave number
as well as the observed H1 NMR chemical
shift in the upfield region in EAA-THF
binary mixture have also been used to
explain the molecular interaction in the
binary liquid mixtures.
ACKNOWLEDGEMENT
RY thanks University Grant
Commission, Government of India for
awarding fellowship. We thank central
facility of IIT Kanpur for giving the chance
to perform the FT-IR and 1H NMR
measurements. We also thank Dr. Pratik
Sen, Department of Chemistry, IIT Kanpur
for providing the UV-Vis spectrophotometer
and spectrofluorometer for absorption and
emission measurement, respectively.
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Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
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Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)
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PriyankaYadav, et al., J. Chem. & Cheml. Sci. Vol.3 (4), 269-276 (2013)
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Journal of Chemistry and Chemical Sciences, Vol.3, Issue 4, 1 October, 2013 (229-279)